Adhesive and method of making



Patented June 2, 1942.

UNITED STATES Pa rs-m" ounce i u annusi'vnannfxitiz onor'mnnic i John w. "was, 111., aim: to United WaIiPaper Factories,v

poration of Delaware Inc., Chicago, 111., a corilo-Drawing". Appllcatlonlii arch a, 193s, l semi No. 197,960

This invention relates to an adhesivewhich is particularlyintended and adapted for use in the wall paper and similar coating industries, while being of general application and utilityas anadhesivep l An object of the present invention is to provide an adhesive-having a corn protein as its base.

Another object of the present inventionis to provide a new and improved adhesive which is especially adapted for usein the wall paper artfor securing pigments upon wall paper and with out interfering with or changinglthe color or shade of such pigments. a c Another object of this invention is to provide an adhesive which is especially adapted for use in the wallpaper and similar coating industries and which can be made water-resistant by the'use of substances heretofore'known but with greater economy than has been.possible heretofore.

An additional objectof the present invention:

cedure outlined in the nextprecedins paragraph f is relatively very expensive or costly from thestandpoint of manufacture and is mechanically cumbersome in use. Accordingly, the research which resulted in the present invention wasin stituted, in part, for thepurpose of ways-and meansof removing the objectionable features which are inherent in the methoddescribedin the next preceding paragraph, of utiliz ing such corn proteins or prolamines as adhesive bases while still retainingthe desirable properties of these substances-including their excellent adhesive properties. v j c a i In the research and experimental work which led up to the present inventiomit was found that corn protein adhesive bases such, for example, as those referred to above, could be put into solution. by using consecutively and separately two dif-i ferent solvents or solvent mixtures, that is, the a corn protein could be put into solution by first thoroughly mashin'g the same in a mixtureconw much larger percentages of protein, and it has been'found that these materials provide an excellent base for an adhesive, and that they have the advantage, over other vegetable adhesive bases such, for example, as peanut meal, soya bean meal, etc., inthat they can be converted into coatings and p ting inkswhich represent distinct economies in nufacture as well as having distinctly improved properties in use. c

It has been found that a large portion of the protein content which is present in such corn derivatives consists of alcohol soluble proteins, known as, prolamines, which are quite different in both chemical composition and properties from othervegetableproteins. f It hasffurther been found that the alcoholsoluble proteins or prolamines, which are derived from corn, can be dissolved in a suitable alcohol such; forv example, as wood alcohol, and that the solution thus prepared can then be emulsified by means of an alkaline resinate or similar emulsifying agent, and blended with a water solution of suitablepigments or otherinertmaterials;

Ithas also been found, however,that the prosisting of alcohol and bleaching agents.

upon the mixture thus formed could be dimolved in water containing a relatively smallamount of, alkali.) However, it was (mind that this"procedure, while retaining the desired solubility of the prolamines, and less cumbersome than v the objectionable ,"alcohol or double solution method hereinbefcre discussed. stillrelatively costly and expensive fromthe standpointof manufacture, in that the cost of the materials was still relatively high, resulting adhesive was too dark inflcolor and would not lend itself readily to being bleached by common.

Further investigation disclosed, however, that the necessity for the use of alcohol could be eliminated entirely, that is, it was found that the corn protein base or meal could readily be'put into solution by mixingthe'saine in a mixture of a resin, such, for example, as ordinary wood rosin, and ammonium hydroxide, thus entirely eliminating the need for the use of alcohol as a solvent, in the mixture, and also eliminatingthe time, labor and expenseinvolved in the cumbersome method of putting the two solvent mixtures, referred to above, together, audit is an object of the present invention to accomplish this ,result of eliminating entirely the need for the alcohol and the two-stage operationof putting the corn protein into solution, in which alcohol has been employed, and to put the corn protein into solu a such, .for example, as wood rosin, and ammonium hydroxide, wheretion by means of asingle solvent without the use 4 of alcohol, and in a one-stage operation. However, it was then discovered that the resulting Hydrogen peroxide (30%)-.

adhesive, while lighter than that which resulted from using alcohol as a solvent and satisfactory, in general, could not be used for the purpose for which it was principally intended, namely, in

coating and printing wall paper and the like, be-

cause it was too dark in color and did not lend itself tobeing bleached by common bleaching h" an adhesive or size which is to Ebe'Iused industries must be very light in "use -c: the necessity for using it freupon papers which are white or have gbthr-lightcolors or shades thereof. thereupon discovered, however, upon j furthefresearch, that this dark colored adhesive, consisting, essentially, ,of a corn protein or meal "base, a resin such, for example, as wood rosin, ammonia and water, could readily be bleached by-the use of common and familiar bleaching 1 agents which are used in the art such, for example, as a water solution of hydrogen peroxide, (HzOz). provided the said adhesive mixture or solution were first heated to a temperature of not substantially less than 170 F. nor substantially more than 210' 1 2, after which the objectionable a darkcolor of the adhesive could be removed by subjecting the same toyarious bleaching agents which are common and well known in the art such, for example, as hydrogen peroxide (H202) it being noted in this connection, that the aforesaid temperature of from approximately 170 F. to approximately 210 1". is not merely arbitrary but has been found by extensive experimentation to be rather critical.

adhesive solution thus prepared may be used in various ways in the wall paper and other Example No. 2

Parts Water 30 to 70 Corn-gluten meal 3 to 8 5 Wood rosin 2 to 'l Ammonium hydroxide (26 B.) 1 to 6 Bleaching powder ...0.1 to 2 EmmpleNo. 3

m 4 Parts Waters. 30 to 70 Corn-gluten meal 3 to 8 Wood rosin 2 to 7 Ammonium hydroxide (26 B.) 1 to 6 Sodium hydrosulphite Na2S2O4 0.1 to 1 paper coating arts, and in various other ways,

such, for example, as a size, but it is principally intended for use as either a'liquid or a dry-adhesive base for the various and numerous colors and pigments which are used in the wall paper art and such, for example, as various clays, lithopone, titanium dioxide, etc., and when so used has been found to be sumciently light in color to meet the requirements of such an adhesive and otherwise a very satisfactory adhesivefor its intended Pu pose. a c v It has also been found that wall paper and other paper coatings and inks prepared in the manner described above, that is, by employing the new adhesive, have superior coating, printing, and drying properties andare relatively mucltliless' expensive in manufacture than the materials employing protein adhesives have been used heretofore. It has also been found that the new adhesive be made water-resistant in a manner and The following examples represent typical formulae which may be followed in preparing the new adhesive, all parts indicated being by weight,

it being understood that the proportions shown are merely illustrative and may be varied considerably:

In preparing the new adhesive according to any of the formulae represented by the foregoing examples, the water, com-gluten meal and the resin, which may be ordinary wood rosin or other resins, natural or synthetic, and the ammonium I hydroxide, are preferably mixed together and the mixture thus formed is then heated to a temperature not substantially less than 170 F. and not substantially greater than 210 F., so as to dissolve the resin in the solution, thus forming a colloidal suspension or emulsion of the corn protein adhesive base in ammoniumresinate, and thereby putting the corn protein base in a condition wherein it may be bleached by the use of such bleaching agents which are well known and commonly used in the art, and examples of which have been given in the foregoing examples. The selected bleaching agent or agents are then added to the ammonium resinate adhesive emulsion, and if the adhesive is intended for use in the wallpaper or analogous paper-coating arts, suitable coating, coloring, or printing materials, such as thosev which will be referred to hereinafter may be added.

It will then be found that the objectionable dark color of the corn protein adhesive base composition may thereupon be removed by the bleaching agent and the composition thus rendered especially satisfactory for use in the wall paper and analogous paper coating arts in which it could not be used except for the heat treatment of the adhesive base and its suspension in an alkaline resinate, in the manner which has been described hereinbefore, as well as being adapted for use as an adhesive, in general.

The new adhesive, prepared in the manner described above, and according to any of the foregoing formulae, may be used, and is especially adapted to be used, in conjunction with various coating, coloring and printing materials which are well known and in common use in the wall paper and allied paper coating arts, as well as in the various other ways in which an adhesive may be used. Thus, for example, to the adhesive composition made according to Example No. 1, thirty (30) parts of coating clay may be added; to the adhesive made according to the formula given in Example No. 2, thirty (30) parts of dry color such, for example, as red turkey umber, ultramarine blue or ferrite yellow may be added; and to. the adhesive prepared according to the formula given in Example No. 3, twenty (20) parts of lithopone may be added, together with 0.5 part of a forty per cent (40%) solution of formaldehyde, in order to increase the water resistant properties of the resulting product.-

Inlplace of the ammonium reslnate solvent which results from mixing a suitable resin, such as wood rosin in, a water solution of ammonia, as specified above, other alkaline resinates may be used as the solvent or: emulsifying agentfor may be manufactured and sold in dryform and the, corn protein base, adhesive and among such mixed at the place of use with from 100 $100 alkaline resinates are sodium resinate andpotasparts of water, whereupon'the liquid thus made slum resinate, and, inmplace of ammonia, ammay be heated and bleached inthemanner here-'= monium linoleate mafbeused for"the purpose inbefore described, and used inariyof the ways of introducingfthe KNHQ) radicaljinto the resin hereinbefore set forth, as well as in other'ways.

solution andfsodium or potassium linoleate may It should also be noted, in thisconnection, that be, used, if desired, fo'r the purposeof introducinplace ofjthe wood rosin and caustic soda set ing either sodium or potassium; ions into the forth in Example No. 4, above any dry alkaline resin solution. However, nothinghasbeen found resinate such, for example, as sodium o'r potaswhich can be used in place of thefammonium resinate, may beusm as,and so asto form, resiriate or other alkaline resinates asthe emulsie th necessary emulsifying agent, when the dry fying agent, that is, for; the :purpose" of putting, adhesi ve base thus prepared is later mixed with the corn protein basematerialor rnealinto the water. h, I h form of a colloidal solutionor suspension, and it It" will be seen, therefore, from the foregoing is believed that. the ,step of so doing, and the description, that the present invention accom method by which t is is accomplished, arenew in plishesits aforesaid intended objects, andother" the art. h e h 5 w objects, and provides ajnewcorn proteinliquid As stated above, the strong, alkalis, such as and dry adhesive base which',,whilebeing capable sodium hydroxide ma potassium hydroxide can 0f useas an adhesive, in general. areiespeciallyt be used, if desired, l but? they jlareless desirable adapted for use inthe manufacture ofwallpaper, than ammonium hydroxide for the purpose of and in analogous papercoating-artaforjholding ,makirig the desired, alkaline resinate emulsion coloring materials, pigments, inks and the likef because they tend to give the,.;resu1ting adhesive upon wallpapenend especiallywhite wallpaper, a darker color than thatwhich results when ism-Q35 asgwell as upon wall, papers and other papers monium hydroxide is used, and hence ammonium havinglight colors andshades of'color. 1'

resinate is the preferred eminsuymg agent, e It'will also be seen from the foregoing ,descrip- 3 cause it gives the resulting adhesive (a desirable tion of thepresentlinvention that the same prolighter color than that which results \t'heneither vides a new method of making a corn protein sodium resinateor potassiumresinate is as adhesive, and whichmethod includes the steps,

" the emulsifying agent; i

v M hh h, believedto be novlibfbutting the corn protein It is tobe noted, in connectionwith the presadhesive into the form of a solutionor colloidal entadhesivej and, the aforesaid method er mak-j suspension by ammdniumresinate or ing' the same, that other protein base materials, other alkaline resinate and removingthe objecandgmeals such, for 'example, as soya bean tlonable darkcolor ;,from the "resinate, emulsion meal, peanutEmeais, and' others, can'notjbe subthus ffotfmedby h i t nt the same to a temperastitutedfor the cornprotein adhesive base or ture of fromapproximately 179 1'', to} approxi meal'which is usedin the manufacture of the mately 210 F., inclusive, dependingXupon the present adhesive, because the essential {and jnecparticularresin and finally bleaching the essary stepof heating the present material up 40 adhesive composition ,thus formed andtreated;

to a temperature of from 170' to 210 F. as While itlmay'be'dispute'das towhether or not 1 described above, to put the' coloring material it is entirely correct torefer to ammonia'and the contained in thecom protein adhesive base, and (NI-I4) radical or ion asan alkali, it is contemineluding the naturally occurring substances .plated and intended that the terms alkali" and chlorophyll and anthocyanin, ina condition "alka1ine lli'lld hfllfiihylhd as used hereinaftnin clalma are' intended to and do inwherein they are attacked -by common andfa-y I h "cludenot only .the"l true such as sodium miliar bleaching agents, such as hydrogen peroxide, will react detrimentally upon the adhesive proteidal substances which are present in'soya bean meal, peanut meal, and the like, and initiate undesired hydrolysis in the same,uand thus lessen their adhesive properties, butsuch heatinghas no detrimental effect uponthe adhesive properties of the corn protein adhesive base which is used in making the present adhesive. i

In addition to being especially adapted for use taupe: "alsoammonia,and'the"(NHQIv radical .o

dil

fa'iid=ipp m; hydroxide, equivalent sub V oorn protein asusedhereinbefore, I hereinafter in the claims, refersnot to cornprotein adhesive basematerial.

example, corn gluten meal which in- L or contains-both the alcohol-soluble corn ,proteinlfprI- fprolamines and the alkali-lemme as a liquid adhesive inthe wallpaper and other w fi l i b but it i! l fid analogous coating arts, as'well as for use as an 93 1 include b dm-p adhesive, in general, the adhesive provided by 4 r v the present invention may also be manufactured fli h fll imusinted ma m" and used as a dry adhesive base, to be later mixed m d the e with water to form a liquid adhesive. Thusla W my invention into satisfactory dry adhesive base jembodyi ng this ramble! ai h phase of the present invention may be made i l v according to the formula represented by the therefore (not wish to be mud following examplegin which all parts indicated detail '01 mpmmon m m at l are by weight:

, forth, but desire to avail myself of departing from the spirit of theginvcnflon. I, i

i tions and modifications as come within the scope 'm 4 PM of the appended claims Corn-gluten meal; 100 ,1 claim: i a w rosin 2 1 1- method of m Caustic mda a t to 15 comprises forming a dispersion of waterymb- I atantially free of alcohol or other organic'sol- I The composition made according to the for vent, a corn'protein base in luflclmqumflty mula represented by the foregoing Example No. 4 t 1 adhesive prom man part adhesive properties to the resulting composition, and an alkaline resinate, then heating the dispersion thus prepared to a temperature not substantially lower than 170 F. nor substantially higher than 210 F., and then adding hydrogen peroxide as a bleaching agent to the dispersion thus prepared and heated.

3. The method of forming an adhesive which comprises forming a dispersion of water substantially free elf-alcohol or other organic solvent, a corn protein base in sui'iicient quantity to impart adhesive properties to the resulting composition, and one or more substances selected from the group consisting of ammonium resinate, sodium resinate, and potassium resinate, then heating the dispersion thus prepared to a temperature not substantially lower than 170 F. nor substantially higher than 210 F., and then adding a bleaching agent to the dispersion thus prepared, at the temperature stated.

4. The method of making an adhesive which comprises forming a dispersion of water substantially ireeof alcohol or other organic solvent, a corn protein base in suillcient quantity to impart adhesive properties to the resulting composition, a, resin, and one or more substances selected from the group consisting of the hydroxides and linoleates of sodium, potassium and the ammonium, or (NHi) ion, then heating the dispersion thusprepared to a temperature of not substantially lower than 170 F. nor substantially higher than 210 F., and then" adding a bleaching agent to the dispersion thus prepared and heated.

5. The method of making an adhesive which comprises forming a dispersion of water sub-- stantially free of alcohol or other organic solvent, a corn protein base in sufllcient quantity to impart adhesive properties to the resulting composition, a resin, and one or more substances selected from the group consisting oi the hydroxides and linoleates of sodium, potassium and the ammonium, or (NH4) ion, thenheating the dispersion thus prepared to a temperature of not substantially lower than 170 F. nor substantially higher than 210 F., and finally adding hydrogen peroxide as a bleaching agent to the dispersion thus prepared and heated.

6. A method of making an'aqueous adhesive composition which "is particularly adapted for use in the manufacture of wall paper and other coated paper products, said method comprising mixing a major portion of water, substantially free of alcohol or other organic solvent, with a relatively smaller portion of a corn protein in a quantity sufficient to impart adhesiveproperties to the resulting, mixture, incorporating with the mixture thus formed one or more dispersing agents selected from the group consisting .of the resinates and linoleates of sodium, potassium and the ammonium (NH4) ion, heating the composition thus formedto a temperature of not substantially lower than F. nor substanti'ally higher than 210 F., and then adding a bleaching agent to the said composition, at the temperature stated, so as to bleach the natural dark color of the said corn protein and thus adapt the adhesive composition thus prepared for maps an adhesive in the manufacture of wall paper and other coated paper products.

JOHN W. CLOSE. 

